Artificial material and method of making same



Patented May 9, 1939 2,157,190

UNITED STATES PATENT OFFlCE ARTIFICIAL MATERIAL AND METHOD OF MAKING SAME George W. Seymour, Cumberland, Md., assignor to C'elanese Corporation of America, a corporation of Delaware No Drawing. Application November 23, 1934, Serial No. 754,472

2 Claims. (Cl. 260-13) This invention relates to the production of artithe purpose of description and the claims, is ficial materials such as filaments, films, foils, termed formal of vegetable oil. Further in sheets, lacquers, etc. that contain an organic accordance with my invention, I add to or inderivative of cellulose and more particularly to corporate with materials containing organic de- 5 such materials which contain besides the organic rivatives of cellulose from less than 1 to 20% or derivative of cellulose a material that lends fiexmore, based on the weight of the organic deibility and elasticity thereto without materially rivative of cellulose, of a formal of vegetable oil. softening same. The incorporation of the formal of vegetable oil An object of the invention is the economic and with the organic derivatives of cellulose is pref- ]o expeditious production of artificial materials that erably accomplished while the organic derivacontain organic derivatives of cellulose that are tive of cellulose is dissolved in a volatile solvent flexible and pliable yet which are not softened apwhich is relatively free from water. preciably by the material that, incorporated Any suitable oil may be employed as one of the therewith, produces these desired qualities. reactants in forming the formal of vegetable oil.

Other objects of the invention will appear from Although it is preferable to employ oxidized castor the following detailed description. oil, with particular reference to which this in- In employing my invention, I add to or incorpo Vention will be described, other oils may be emrate with the organic derivative of cellulose a D y instance, Castor OiLSOya bean OiLOliVB reaction product of a vegetable oil and a comoil, teaseed oil and other non-drying or semi-dry- 29 pound containing an aldehyde radical, In this ing oils that contain at least some constituents manner I am able to produce hard filaments, containing a hyd o y group, and also Such 011$ films, foils, etc. that are pliable and elastic yet which after they have been oxidized contain a which retain their original transparency. Thus, y y p. he O l ater a is reacted With by employing this invention tougher films and a p u d Containing a least e a d yde filaments may be produced than was heretofore ca for instance, formaldehyde, D y possible. metaldehyde, acetaldehyde, crotonic aldehyde,

Filaments produced according to this invention c.

ar pliable and may b circul knitt d int The reaction between the oil and the aldehyde fabric of exceedingly fine stitch shape without m y be Carried out by r fl xin the two materials 30. breaking since the filaments are rendered amenliOgether in the presence of a Catalyst, for amable to the back and forth bending through P phosphoric acid- The proportion of yd sharp angles occurring during the knitting oper- Calculated as formaldehyde, Oil y be om ation. less than 1 to more than 3 times the theoretical Films and foils produced according to this inamount to form the Cllethel" 0f e aldehyde 5 ti may b h d yet pliable d are t d radical with the hydroxyl radicals of the oil, as-

' less transparent by reason of the incorporated Sllmihg the Oil to be the p glyceride Of a fatty material that produces these qualities. Further, acid- 111 Employing Oxidized C st O a d formthe added material or modifying material is comaldehyde, the preferable Portion may be 00 patible with the solution from which the fila- Parts Of Oil by Weight 30 p Of yde 4Q, ments, films, foils, etc. are formed. Solutions, by Weigh T e eflux y e carried out at 6 therefore, may be made that are stable and capafrom less than 130 Over d or a ble of storage and handling, as solutions, with length of time to complete the reaction, which out the precipitation of one or the other of the may be from 4 to 10 hours- By t process bcomponent5 stantially all the aldehyde compound enters the h invention is l dir t t t reaction leaving but a trace of unreacted aldepounds that impart to filaments, films, foils, etc. hydeof organic derivatives of cellulose pliability and In the preparation of a formal Of a ble flexibility without materially reducing the hardoil, emp y Castor i f instance, h pr ness of the material or reducing its transparency. Cedllre may Consist in refluxing the sto Oil in These compounds are the reaction product of the presence of a catalyst with more than 3 times 5 oxidized vegetable oils with aldehydes. the theoretical amount of paraform to form the In accordance with my invention, I react a diether by reaction between the aldehyde radicals compound containing at least one aldehyde radiand the OH radicals of the oil, assuming the oil to cal with a vegetable oil, oxidized vegetable oil be the pure glycerol triricinoleate, washing with or a mixture of these. The resulting product, for cold water to remove the catalyst, then with hot 55 water to remove the residual trace of paraform and finally drying the oil in the presence of ethyl alcohol. The product may be subjected to steam distillation prior to treatment with alcohol. The resulting product is an oily appearing substance, usually brown in color, having an increased viscosity over the starting oil. The product may have a very marked sweet aromatic odor. The product is compatible with solutions of organic derivatives of cellulose, especially when the solution of the organic derivative of cellulose is comparatively free from water.

As an illustration and not as a limitation, the following example of producing the formal of vegetable oil is given.

Example I Parts by weight .Oxidized castor oil 100 Paraform aldehyde (3 aldehyde radicals) 30 Phosphoric acid 0.2

are refiuxed for about 8 hours at from 100 to 120 C. The product is then steam distilled for about 8 hours, washed with cold water to remove phosphoric acid and then dried in the presence of either ethyl or methyl alcohol. The product is a clear brown liquid having a sweet aromatic odor.

The formal of vegetable oil may be incorporated with organic derivatives of cellulose in amounts of up to and over 20% of the weight of the organic derivative of cellulose. This results in films and filaments possessing a marked flexibility which is not ordinarily attainedin like articles of an equal degree of hardness. Any suitable organic derivative of cellulose may be employed as the base material such as the organic esters of cellulose and the cellulose ethers. Examples of organic esters of cellulose are cellulose acetate, cellulose formate, cellulose propionate and cellulose butyrate, while examples of cellulose ethers are ethyl cellulose, methyl cellulose and benzyl cellulose.

The organic derivatives of cellulose may be dissolved in any suitable solvent, and especially a solvent containing no water. For instance, in employing cellulose acetate, there may be used a mixture of equal parts of acetone and methylene ether of ethylene glycol as the solvent. Other solvents may be employed, for example, a mixture of acetone and ethyl or methyl alcohol, ethylene dichloride, a mixture of ethylene dichloride and ethyl or methyl alcohol, and like solvents. When making filaments, films, foils, etc. from such solution there may be added, besides the formal of vegetable oil, any desired modifying agent by which term is meant an agent that modifies the lustre, hardness, color, etc. of the resulting filament, foil, film, etc. Examples of modifying agents are pigments, filling materials, dyes or lakes, fire retardants, plasticizers, sizes and lubricants.

Filaments may be formed from the solutions containing the organic derivative of cellulose and formal of vegetable oil by any suitable method. Thus, when employing cellulose acetate a solution may be formed of about 1 part of cellulose acetate, 4 parts of solvent and 0.2 part of formal of vegetable oil, and the same extruded through suitable orifices into a solvent removal medium, such as an evaporative atmosphere in the dry method of spinning, or a precipitating bath in the wet method of spinning. Any suitable method of spinning may be employed, many of which are well known in the art. Any amount of formal of vegetable oil may be employed preferably from less than 1 to about 20%, when clear, tough films are desired. A similar solution with or without the addition of modifying agents may be cast on a surface such as a film casting wheel and the solvent removed to form films or foils. Further, sheets may be formed of the mixture of organic derivative of cellulose and formal of vegetable oil by block pressing methods, i. e. a large block or rod formed by pressing the plastic material in the presence of heat is cut into sheets by a planer or lathe type of sheet cutting device.

As an illustration and not as a limitation the following example of forming films is given:

Example II A solution or mixture is formed by mixing together The mixture is then flowed upon a polished surface such as a film casting wheel and the volatile material removed, after which it is stripped from the wheel. The film is clear and tough with a marked degree of flexibility for its hardness.

In place of adding the formal of vegetable oil to the solution from which films and filaments are formed, the formal of vegetable oil may be incorporated with formed films or filaments by coating same with the formal of vegetable oil in the presence of a swelling agent for the base material of the film or filament. Further, the formal of vegetable oil may be mixed with untreated or oxidized oil to form a lubricant for filaments.

It is to be understood that the foregoing detailed description is merely given by way of illustration, and many alterations may be made therein without departing from the spirit of my invention.

Having described my invention, what I desire to secure by Letters Patent is:

1. A composition of matter comprising cellulose acetate and from 2 to 10%, based on the weight of the cellulose acetate present, of the reaction product of 100 parts by weight of oxidized castor oil and 30 parts by weight of paraformaldehyde.

2. Filaments, films and other artificial mate-- rials comprising cellulose acetate and from 2 to 10%, based on the weight of the cellulose acetate present, of the reaction product of 100 parts by weight of oxidized castor oil and 30 parts by weight of paraformaldehyde.

GEORGE W. SEYMOUR. 

